Tribol Lett (2014) 56:133–142
DOI 10.1007/s11249-014-0392-2
ORIGINAL PAPER
Effect of Graphene and Ionic Liquid Additives on the Tribological
Performance of Epoxy Resin
N. Saurı́n • J. Sanes • M. D. Bermúdez
Received: 4 June 2014 / Accepted: 6 August 2014 / Published online: 21 August 2014
Ó Springer Science+Business Media New York 2014
Abstract In the present study, we have determined the
effect of graphene (PG), the ionic liquid (IL) and PG
modified by mechanical blend with the IL 1-octyl-3-
methylimidazolium tetrafluorobotate (IL ? PG) on the
tribological performance of epoxy resin (ER). IL ? PG
stable suspensions have been added to an epoxy resin (ER)
matrix to obtain the new nanocomposite (ER ? IL ? PG),
and its tribological performance has been compared with
that of neat epoxy resin and with the nanocomposites
containing PG (ER ? PG) or IL (ER ? IL). While neat ER
presents a high dynamic friction coefficient of up to 0.31
and a severe wear with a specific wear rate of 8.1 9 10-4
mm3 N-1m-1, the new nanocomposites show negligible
surface damage, as determined by surface roughness and
profilometry. All nanocomposites show low friction coef-
ficients and negligible wear. The maximum friction
reduction, up to a 70 %, is obtained for ER ? PG. Results
are discussed upon the basis of TEM microscopy, SEM
microscopy and EDX analysis, differential scanning calo-
rimetry, thermogravimetric analysis and dynamic
mechanical analysis. Addition of IL or IL ? PG has a
plasticizing effect on ER, while addition of PG increases
the thermal stability and stiffness of ER. PG shifts the
storage modulus onset and in the loss modulus and tan d
maximum peaks to higher temperatures, while a shift to
lower values is observed with addition of IL or IL ? PG.
N. Saurı́n
J. Sanes
M. D. Bermúdez (&)
Grupo de Ciencia de Materiales e Ingenierı́a Metalúrgica,
Departamento de Ingenierı́a de Materiales y Fabricación,
Universidad Politécnica de Cartagena, Campus de la Muralla del
Mar. C/Doctor Fleming, s/n, 30202 Cartagena, Spain
e-mail: mdolores.bermudez@upct.es
Keywords Epoxy resin
Ionic liquid
Graphene

Nanocomposites
Dynamic friction
Wear and lubrication
1 Introduction
Tribology of polymers and polymer-matrix composites is
increasingly relevant due to their growing applications in
sliding parts, as surface finishing materials and in self-
lubricating components [1–5]. Polymer composites con-
taining graphene (PG) are an active research field due to their
improved mechanical, thermal and electrical properties [6–
11]. Epoxy resin nanocomposites containing PG or graphene
oxide are currently the object of great attention due to their
enhanced mechanical or electrical performance [12].
Room temperature ionic liquids (ILs) have shown an
outstanding lubricating performance for metals, polymers
and ceramic materials under severe conditions [13–18] due
to their ability to form ordered adsorbed tribolayers.
We have previously described [19, 20] the friction and
wear reduction of epoxy resin by external lubrication or by
addition of ILs. A very recent research [21] has shown that
ILs can act as cross-linkers of epoxy resin and as disper-
sants of graphite nanoplatelets in an epoxy matrix.
Graphene, constituted by one-atom thick layers of sp2
carbon, has risen and extraordinary scientific and technical
interest [22, 23]. The tribological and surface science
applications of PG are some of the most front edge lines of
research at the present moment.
There exist very few precedents of the use of PG in
friction and wear reduction [23, 24].
Choudhary et al. [25] have reported a 26 % friction
reduction and a 9 % wear reduction for steel by lubrication
with hexadecane containing chemically modified PG, which
is supposed to intercalate between the sliding surfaces.
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134 Tribol Lett (2014) 56:133–142

Fig. 1 TEM micrographs: a,

b as-received graphene (PG);
c IL ? PG; d ER ? PG;
e ER ? IL ? PG

Kandanur et al. [26] have shown that the wear rate of the PG sheets could reduce wear by inhibiting crack
polytetrafluoroethylene (PTFE) is reduced in four orders of propagation.
magnitude by addition of a 10 % of PG sheets of 3–4 layers The present work was carried out in the expectation that
as nanoreinforcements. These authors have proposed that the reinforcing effect of PG and the dispersing ability of

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Tribol Lett (2014) 56:133–142 135

PG was added to the prepolymer) were processed as previ-

1.0 IL + PG ously described [19, 20]. In order to obtain ER ? 9 wt%
PG
IL ? 0.1 % PG (ER ? IL ? PG), PG (0.1 g) was added to
0.8 IL (9.0 g) and the mixture was mechanically stirred in an
agate mortar for 5 min and then at 1,600 rpm for 30 s to
Normalized intensity

0.6
obtain IL ? PG which was added to the prepolymer before
processing following the method described [19, 20].
SEM images were obtained using a Hitachi S3500N.
0.4
The epoxy samples were platinum-coated with a SC7640
Sputter Coater before observation. TEM micrographs were
0.2 obtained with a high-resolution JEOL JEM 2100. Raman
spectra were collected using a Nicolet Almega XR Raman
0.0
spectrometer from Thermo Electron, equipped with an
0 1000 2000 3000 Olympus microscope. A laser of 514 nm at 100 % of
-1
Wavenumber (cm ) power and 50 lm of aperture was used. A differential
scanning calorimeter (DSC) 822e (Mettler-Toledo) was
Fig. 2 Raman spectra of as-received PG and IL-modified graphene used to determine glass transition temperatures (Tg); 15 mg
(IL ? PG)
samples were heated under an inert N2 atmosphere
(50 ml min-1), at a heating rate of 10 °C min-1. Degra-
Table 1 Raman spectroscopy data dation temperatures (Td) were determined in air with a
Material D band G band 2D band ID/IG I2D/IG Shimadzu thermogravimetric analysis (TGA)-50 equip-
(cm-1) (cm-1) (cm-1) ment (20 °C min-1; N2, 40 ml min-1). Dynamic mechan-
PG 1,358.3 1,581.8 2,721.8 0.16 0.52
ical analysis (DMA) under the dual-cantilever clamping
mode was carried out on prismatic test specimens
IL ? PG 1,356.7 1,583.3 2,728.3 0.28 0.52
(dimensions 17 9 3.8 9 3.3 mm) with a TA Q800 DMA
analyser equipped with a TA Universal Analysis 2000
ILs could also improve the poor tribological performance software. Glass transition temperature (Tg) values were
of epoxy resin. determined at an oscillatory frequency of 1 Hz, under a
Chemical modification of PG has been described by 1 % strain, for a temperature range from 30 to 120 °C at a
covalent and non-covalent interactions. However, covalent heating rate of 3 °C min-1.
modifications can modify the PG conjugation system and, Pin-on-disc tests were carried out with a ISC 200-PC
consequently, its properties. Non-covalent modification by pin-on-disc tribometer using discs (diameter 40 mm;
p–p stacking and van der Waals interactions is believed to thickness 4 mm) against AISI 316L stainless steel balls
maintain the structure and properties of PG [27]. In the (hardness 210 HV) with a 0.8 mm sphere radius, under dry
present study, non-covalent interactions between PG and conditions, that is, without external lubrication. Normal
IL have been produced under mild conditions. applied load was 0.49 N (mean contact pressure 0.07 GPa),
The IL selected for the present study combines a high sliding velocity 0.10 ms-1, sliding distance 500 m and
thermal stability with a high molecular polarity, which allows sliding radius 9 mm. The 500 m sliding distance allows a
the formation of adsorbed layers on metal surfaces, and the steady state regime to be reached for all materials studied.
presence of a long alkyl side chain which could improve the Wear rates were determined by means of a Talysurf CLI
compatibility of nanophases with the polymer network. profilometer. At least three tests were performed under the
To the best of our knowledge, the present study is the same experimental conditions for each material, at room
first on the tribological properties of epoxy resin-PG or temperature with a relative humidity of 40 ± 5 %. Steel
epoxy resin IL-modified-PG nanocomposites. balls were observed by optical microscopy (Leica DMRX).

2 Experimental
3 Results and Discussion
1–2 Layers PG (Avanzare Nanotechnology; Spain) and the
IL 1-octyl-3-methylimidazolium tetrafluoroborate (Fluka, 3.1 TEM Microscopy
Germany) ([98 % purity) were used as-received. ER and
ER ? 9 wt% IL (ER ? IL) were prepared following a pre- Figure 1a shows a TEM micrograph of the as-received PG
viously described method [19]. ER ? PG (where a 0.1 wt% sheets. Figure 1b shows the ordered structure present in the

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136
C 1s
286.7
686.1
F1s
194.2
B1s
Fig. 3 XPS analysis of neat IL
ionic liquid-modified graphene IL ? PG. The different
stacking of PG layers in Fig. 1d as compared to Fig. 1c
could be attributed to a possible exfoliating effect of the IL
on PG [28]. ER ? PG (Fig. 1e) shows the presence of PG
platelets similar to those present in PG (Fig. 1b).
3.2 Raman Spectroscopy
Figure 2 shows the G band, characteristic of in-plane
vibrations of the graphitic wall, at 1,581.8 cm-1 (Table 1).
The D band for PG is observed at 1,358.3 cm-1 (Table 1).
The low ID/IG intensity ratio of 0.16 is indicative of a rela-
tively low proportion of defects. The 2D band, characteristic
of PG, which originates from second-order Raman scattering
process [29], appears at 2,721.8 cm-1. Graphene bands in
the ER ? PG nanocomposite cannot be analysed due to the
absorptions of the epoxy resin in the same region.
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Tribol Lett (2014) 56:133–142
285.0
401.95
N1s
532.4
O1s
3.3 XPS Analysis
Figure 3 shows the binding energies for C1s, F1s, N1s and
B1s present in neat IL. The O1s peak observed at 532.4 eV
could be attributed to water impurities present in the IL.
Figure 4 shows the corresponding binding energies for
IL ? PG. F1s, N1s and B1s peaks are similar to those found
for neat IL and show the surface modification of PG by IL.
The main differences are observed for C1s and O1s peaks.
Neat IL shows a C1s peak at 285.0 eV assignable to the
aliphatic carbon (and also to carbon impurities) atoms
present in the alkyl substituents of the imidazolium ring. The
same peak is present in IL ? PG. The C1s peak of neat IL at
286.7 eV is assignable to the sp2 carbon atoms of the imi-
dazolium ring. In the case of IL ? PG, two peaks assignable
to sp2 carbon atoms are observed at 286.2 and 287.4 eV,
respectively, which could be assigned to the imidazolium
Tribol Lett (2014) 56:133–142
Fig. 4 XPS analysis of
IL ? PG
C 1s 2
686.8
F1s
194.85
B1s
ring and PG, respectively. A new O1s peak is observed in
IL ? PG at 533.9 eV. This could be tentatively assigned to
graphene oxide residues present in the commercial PG used.
3.4 Nanophase Distribution
Previous studies [19] on ER ? IL nanocomposites have
shown a uniform distribution of ILs in the epoxy matrix.
Figure 5 shows the fracture surface of ER ? IL (Fig. 5a)
and ER ? IL ? PG (Fig. 5b). In both cases, the fluorine
element maps show a uniform distribution of the additives
in small rounded particles. In the case of ER ? IL ? PG,
the uniform distribution is attributed to surface modifica-
tion and partial exfoliation of PG by IL, although some
larger size agglomerates are also present (Fig. 5b).
137
285.0
286.2
287.4
402.7
N1s
533.9
O1s
532.2
3.5 Thermal Properties
Table 2 compares the thermal properties [30] of the new
nanocomposites with those of the epoxy resin. ER ? PG
presents a glass transition temperature of 90.3 °C, similar
to that of ER (91.9 °C), and shows a higher thermal sta-
bility, with a degradation temperature (for a 50 % weight
loss) of 348.4, 4.5 °C higher than that of ER (343.9 °C). In
contrast, the addition of IL lowers the glass transition
temperature both in ER ? IL and ER ? IL ? PG, while
maintaining a similar or even higher degradation temper-
ature, due to the high thermal stability of the additives.
These results show that IL or IL ? PG have a plasticizing
effect on the epoxy resin, thus increasing chain mobility.
The experimental conditions used in the present case
were selected in order to compare the thermal behaviour of
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138 Tribol Lett (2014) 56:133–142

Fig. 5 SEM micrograph and

fluorine element map of the
fracture surface of: a ER ? IL;
b ER ? IL ? PG

Table 2 Thermal properties those of the neat epoxy resin (Fig. 6). The addition of a
0.1 wt% PG to epoxy resin to give ER ? PG increases
Material Glass transition Degradation (50 % weight
temperature Tg (°C) loss) temperature, Td (°C)
the onset of the storage modulus from 940.6 MPa
(DSC) (TGA) (60.45 °C) to 1,126.0 MPa (64.96 °C) (Fig. 6a). In
contrast, the addition of IL (ER ? IL) reduces the
ER 91.9 343.9 storage modulus to 820.3 MPa (48.61 °C). Loss modu-
ER ? PG 90.3 348.5 lus (Fig. 6b) and tan d (Fig. 6c) peaks are both shifted
ER ? IL ? PG 68.7 327.6 to lower values by addition of IL. ER ? IL ? PG
ER ? IL 68.5 352.5 shows a storage modulus similar to that of ER due to
the opposite effect of the additives present in the
the new blends with that of the neat epoxy resin. Further nanocomposite. These results confirm the reinforcement
studies on thermal stability using low scanning rates or effect of PG even in a very low concentration, while
isothermal conditions [31] will be carried out in order to the presence of the fluid phase in ER ? IL results in a
determine their long-term stability. lower stiffness.
The higher stiffness of ER ? PG could anticipate a
3.6 Dynamic Mechanical Properties good tribological performance by preventing the crack
propagation and fracture mechanisms which are readily
The dynamic mechanical properties of the new nano- produced in neat epoxy resin, as will be discussed in the
composites have been determined and compared with following section.

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Tribol Lett (2014) 56:133–142 139

(a) (a)
10000 0.18
ER
ER + PG 0.16
ER + IL
Storage modulus E' (MPa)

ER + IL + PG 0.14
1000

Friction coefficient
0.12

0.10
100
0.08

0.06
10
0.04

0.02
1
20 40 60 80 100 120 0.00
ER ER+PG ER+IL ER+IL+PG
Temperature (ºC)
(b)
(b) 0.35
350 ER
ER 0.30 ER + PG
300 ER + PG ER + IL + PG

Friction coefficient
ER + IL ER + IL
0.25
Loss modulus E'' (MPa)

ER + IL + PG
250
0.20
200
0.15
150
0.10
100

50 0.05

0 0.00
0 100 200 300 400 500
-50 Distance (m)
20 40 60 80 100 120
Temperature (ºC) Fig. 7 a Mean friction coefficient values after three tests; b repre-
sentative friction coefficient–distance curves
(c)
1.4
ER
ER + PG
1.2
ER + IL
materials containing IL show a very similar behaviour,
1.0
ER + IL + PG with a friction reduction of a 27 % with respect to ER.
Even more significant is the observation of the real-time
0.8
friction–distance curves (Fig. 7b). ER presents a maximum
tan Delta

0.6 friction value of 0.31 after 200 m, to reach a steady state

friction value of 0.27 until the end of the test. ER ? PG
0.4
maintains the lowest friction along the test. A maximum
0.2 friction reduction of a 70 % is obtained for ER ? PG with
0.0 respect to ER. The main advantage in the performance of
ER ? PG with respect to the rest of materials is the
-0.2
20 40 60 80 100 120 140 absence of the initial friction increasing period before
Temperature (ºC) reaching the stationary regime.
The similar behaviour of ER ? IL and ER ? IL ? PG
Fig. 6 Dynamic mechanical properties of ER and the nanocompos- could be attributed to the lubricating performance of IL,
ites: a storage modulus; b loss modulus; c tan d
which predominates over the effect of PG, due to its much
higher relative proportion.
ER shows a very severe surface damage after sliding
3.7 Tribological Performance against the steel ball (Fig. 8a), with a wide wear track
(wear rate 8.1 9 10-4 mm3 Nm-1) covered by wear
Figure 7a shows the mean friction coefficients for the debris.
epoxy resin and the nanocomposites. The maximum fric- As the nanocomposites present no wear rate, surface
tion reduction, of a 53 %, is obtained for ER ? PG. The roughness has been measured in order to quantify surface

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Fig. 8 SEM micrographs and

surface topography profiles after
the tribological tests: a ER;
b ER ? PG; c ER ? IL;
d ER ? IL ? PG

changes with the tribological tests. SEM and profilometry
observations (Fig. 8) confirm the wear prevention effect of
the additives with respect to neat ER (Fig. 8a). ER ? PG
(Fig. 8b) maintains a constant value of 0.14 lm on the
contact region, before and after the test. This confirms the
high-load-carrying ability of the new nanocomposite.
ER ? IL (Fig. 8c) shows a maximum increase in surface
roughness from 0.06 to 0.26 lm, due to the presence of
microcracks which form in the absence of the reinforce-
ment effect of PG. ER ? IL ? PG (Fig. 8d) shows a mild

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polishing effect with a reduction of roughness from
0.09 lm before the test to 0.05 lm after the test.
SEM and profilometry observation confirm the absence
of wear on ER ? PG, which is free from cracks and wear
debris, as compared to ER (Fig. 8b). A similar absence of
surface damage is observed for ER ? IL (Fig. 8c) and
ER ? IL ? PG (Fig. 8d).
4 Conclusions
Addition of 0.1 wt% PG to epoxy resin shifts the onset of
storage modulus, and the maximum of loss modulus and
tan d to higher temperature values, while reducing the
friction coefficient of epoxy resin against stainless steel,
and preventing surface damage or wear.
1-Octyl-3-methylimidazolium tetrafluoroborate ionic
liquid shows an outstanding friction-reducing and antiwear
performance for the epoxy resin-stainless steel contact,
which can be further improved by addition of a 0.1 wt%
proportion of PG.
It is suggested that the reinforcement effect of PG would
be responsible for the good tribological performance, while
the increase in polymer chain mobility and the ability of IL
molecules to form ordered adsorbed tribolayers would
account for the good results obtained for ER ? IL.
The nanocomposite-containing PG surface modified by
the ionic liquid shows a uniform distribution of the
nanophase, with similar thermal, dynamic mechanical and
tribological properties to that of epoxy resin ? ionic
liquid material, where the ionic liquid acts as a plasti-
cizing agent, increasing chain mobility, reducing glass
transition temperature and shifting the storage modulus
onset and the loss modulus and tan d peaks to lower
temperatures.
The combination of PG and ionic liquid could be used in
the development of new nanolubricants and nanocompos-
ites with tailored thermal, mechanical and tribological
behaviour, following the simple method described herein.
Further studies are needed in order to determine the long-
term stability and tribological performance of the disper-
sions and nanocomposites.
Acknowledgments The authors thank the financial support of the
Ministerio de Economı́a y Competitividad (MINECO, Spain)
(MAT2011-23162). N. Saurin is grateful to MINECO (Spain) for a
FPI research Grant (BES-2012-056621).
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